tert-Butyl hydroperoxide → 1-(3-Methylanilino)-4-([1,3,5]trioxan-2-yl)phthalazine

HRID 2119299Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 2119299
[CH3:1][C:2]1[CH:3]=[C:4]([CH:16]=[CH:17][CH:18]=1)[NH:5][C:6]1[C:15]2[C:10](=[CH:11][CH:12]=[CH:13][CH:14]=2)[CH:9]=[N:8][N:7]=1.[O:19]1[CH2:24][O:23][CH2:22][O:21][CH2:20]1.FC(F)(F)C(O)=O.C(OO)(C)(C)C>C(#N)C>[CH3:1][C:2]1[CH:3]=[C:4]([CH:16]=[CH:17][CH:18]=1)[NH:5][C:6]1[C:15]2[C:10](=[CH:11][CH:12]=[CH:13][CH:14]=2)[C:9]([CH:20]2[O:21][CH2:22][O:23][CH2:24][O:19]2)=[N:8][N:7]=1

Komponenten

6

Edukt 4

HCID 6410tert-Butyl hydroperoxideHCID 6422Trifluoroacetic acidHCID 80811,3,5-TrioxaneHCID 223864691-(3-Methylanilino)phthalazine

Produkt 1

HCID 223864601-(3-Methylanilino)-4-([1,3,5]trioxan-2-yl)phthalazine

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6342AcetonitrileLösungsmittel

Reaktionsbedingungen

Temperatur
80 °C

Versuchsvorschrift

To a suspension of 9.6 g (40.8 mmol) 1-(3-methylanilino)phthalazine and 173 g 1,3,5-trioxane in 570 ml acetonitrile, 3.12 ml (40.8 mmol) trifluoroacetic acid, 11.0 ml (80% in tBuOOtBu; 87.4 mmol) tBuOOH and 190 mg (0.68 mmol) FeSO4·7 H2O are added, and the mixture stirred for 17 h at 80° C. The cooled reaction mixture is partly evaporated in the RE, diluted with EtOAc and water and adjusted to an alkaline pH with 1 N NaOH. The aqueous phase is separated off and twice extracted with EtOAc. The organic phases are washed twice with water and brine, dried (Na2SO4) and evaporated. Column chromatography (SiO2; EtOAc/toluene 1:3; applied as solution in dichloromethane/acetone 9:1) yields the title compound after crystallization with the addition of DIPE; m.p. 161° C.; DC (EtOAc/toluene 1:3) Rf=0.27; 1H-NMR (DMSO-d6) 9.27 (s, HN), 8.74 (m, 1H), 8.61 (m, 1H), 8.00 (m, 2H), 7.72 (s, 1H), 7.68 (d, 1H), 7.25 (t, 1H), 6.89 (d, 1H), 6.39 (s, 1H), 5.47 (d, 2H), 5.41 (d, 2H), 2.33 (s, 3H); FAB-MS (M+H)+=324; anal. calc.(C18H17N3O3) C, 66.86%; H, 5.30%; N, 13.00%; meas. C, 66.83%; H, 5.36%; N, 12.81%.

Aufarbeitung

  1. additionare added
  2. customThe cooled reaction mixture
  3. customis partly evaporated in the RE
  4. additiondiluted with EtOAc and water
  5. customThe aqueous phase is separated off
  6. extractiontwice extracted with EtOAc
  7. washThe organic phases are washed twice with water and brine
  8. dry with materialdried (Na2SO4)
  9. customevaporated

Quellen und Nachweise

ORD-Eintrag
ord-a5a25217decf467a8f207f1729d48ae1
Quelldatensatz
uspto-grants-2004_02
Patentnummer
US06686347B2

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